CN103638830B - For the preparation method of the hot method Pvdf Microporous Hollow Fiber Membrane of drinking water treatment - Google Patents
For the preparation method of the hot method Pvdf Microporous Hollow Fiber Membrane of drinking water treatment Download PDFInfo
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- CN103638830B CN103638830B CN201310712323.9A CN201310712323A CN103638830B CN 103638830 B CN103638830 B CN 103638830B CN 201310712323 A CN201310712323 A CN 201310712323A CN 103638830 B CN103638830 B CN 103638830B
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- 239000012528 membrane Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 33
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 27
- 239000003651 drinking water Substances 0.000 title claims abstract description 22
- 235000020188 drinking water Nutrition 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000835 fiber Substances 0.000 claims abstract description 30
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 25
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 25
- 238000000605 extraction Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims abstract description 10
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims abstract description 10
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims abstract description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 9
- 239000001110 calcium chloride Substances 0.000 claims abstract description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 8
- 239000012498 ultrapure water Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 230000000873 masking effect Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 2
- 230000006750 UV protection Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 abstract description 2
- 230000004224 protection Effects 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract description 2
- 239000002033 PVDF binder Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 230000004907 flux Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
The present invention relates to a kind of preparation method of the hot method Pvdf Microporous Hollow Fiber Membrane for drinking water treatment, belong to UF membrane and technical field of drinking water treatment.Kynoar and polyether sulfone are dried, carry out after Kynoar, polyether sulfone, PEG400, triethyl phosphate and calcium chloride are weighed in proportion stirring, dissolving, after feeding double screw extruder is extruded, form the as-spun fibre of hollow, make its cooling curing in cold extraction liquid bath, immerse in ultra-pure water again and remove diluent, dry and obtain Pvdf Microporous Hollow Fiber Membrane.This method uses materials safety health, and environmental protection, has higher heat resistance and chemical stability, outstanding weatherability, resistance to ozone, ultraviolet resistance radiation and chemical resistance, film retain height, to produce water water quality good, not fracture of wire in using, stable performance.It is the high-end drinking water treatment membrane material of function admirable.
Description
Technical field
The present invention relates to a kind of preparation method of the hot method Pvdf Microporous Hollow Fiber Membrane for drinking water treatment, particularly relate to a kind of thermally induced phase separation (being called for short hot method) and prepare Kynoar (PVDF) hollow-fibre membrane blended with polyether sulfone (PES), for municipal drinking water process, belong to UF membrane and technical field of drinking water treatment.
Background technology
The existing water source of China is generally subject to organic pollution, and the combined pollutions such as high organic matter, high concentrtion appear in some areas.Traditional coagulation-precipitation-filtration-sterilization process filtering accuracy is low, disinfectant and coagulant use amount high, large to water quality impact, the water after process can not meet the requirement of new national standard 106 drinking water standards.Membrane separation technique carries out drinking water deep purification now, ensures the important new technology of water quality safety.Be that the water treatment technology of core has developed into third generation drinking water purification process with milipore filter, the group technology of it and other technology, can process micro polluted source, the drinking water of production high-quality effectively.
Traditional non-solvent phase method (abbreviation wet method) produce hollow-fibre membrane, intensity is low, toughness is poor, easy fracture of wire in using, life-span be short, be unsuitable for applying in large-scale drinking water treatment engineering.The hollow fiber ultrafiltration membrane of the large flux of municipal drinking water process, high strength, antipollution, low cost is suitable in the urgent need to exploitation.
Summary of the invention
The object of the invention is the preparation method proposing a kind of hot method Pvdf Microporous Hollow Fiber Membrane for drinking water treatment, the hollow-fibre membrane of preparation high strength, high tenacity, large flux, and make it have stronger contamination resistance, there is higher cost performance, for municipal drinking water process engineering provides product guarantee.
The preparation method of the hot method Pvdf Microporous Hollow Fiber Membrane for drinking water treatment that the present invention proposes, comprises the following steps:
(1) Kynoar and polyether sulfone are carried out drying respectively in dryer, the temperature of oven dry 80 ~ 90 DEG C, drying time is 24 ~ 36 hours;
(2) for the preparation of the blended polymer solution of masking:
In blended polymer solution, the mass percent of each component is:
After Kynoar, polyether sulfone, PEG400, triethyl phosphate and calcium chloride are weighed according to the above ratio, be placed in stirred tank, carry out stirring, dissolving at the temperature of 140 ~ 155 DEG C, mixing time is 14 ~ 16 hours, speed of agitator 90 ~ 110 revs/min, makes uniform blended polymer solution;
(3) the extruding and be shaped of hollow-fibre membrane, detailed process is as follows:
(3-1) blended polymer solution in step (2) is sent in double screw extruder by spinning pump, the charging rate of raw material is 15 ~ 20Kg/ hour, the temperature of extruder 6 sections all sets unanimously, it is 140 ~ 155 DEG C, extrusion temperature scope is 140 ~ 155 DEG C, and screw speed is 90 ~ 120 revs/min;
(3-2) blended polymer solution is after double screw extruder is extruded, successively through filter and spinning pump, extrude from the annular die of spinning-drawing machine, form the as-spun fibre of hollow, the external diameter of described annular die is 5 millimeters, internal diameter is 4.2 millimeters, and annular die center passes into nitrogen, and the pressure of nitrogen is 30 ~ 60 millimeter of water (mmH
2o);
(3-3) above-mentioned hollow as-spun fibre is lower the temperature in the air of 10 ~ 20 DEG C in temperature, the distance that sky is walked is 10 ~ 30 centimetres, then enter in cold extraction liquid bath through cold extraction liquid cooling curing, through winder rolling, make hollow-fibre membrane intermediate, the rolling speed of winder 15 ~ 20 ms/min, described cold extraction liquid is the mixed liquor of water and glycerine, in mixed liquor, the mass percent concentration of water is 0 ~ 50wt%, the mass percent concentration of glycerine is 50 ~ 100wt%, and the temperature of mixed liquor is 30 ~ 40 DEG C;
(4) hollow-fibre membrane intermediate step (3) obtained immerses in ultra-pure water, and remove the diluent mixture in film, the water temperature of ultra-pure water is 30 ~ 45 DEG C, and ultrapure electrical conductivity of water is 10 μ S/cm, and leaching time is 10 ~ 12 hours;
(5) the hollow-fibre membrane intermediate removing diluent of step (4) is at room temperature dried, obtain Pvdf Microporous Hollow Fiber Membrane.
The preparation method of the hot method Pvdf Microporous Hollow Fiber Membrane for drinking water treatment that the present invention proposes, its advantage is:
1, in the inventive method, the material preparing Pvdf Microporous Hollow Fiber Membrane adopted, safety and sanitation, environmental protection, there is higher heat resistance and chemical stability, outstanding weatherability, resistance to ozone, ultraviolet resistance radiation and chemical resistance are the high-end drinking water treatment membrane materials of function admirable.
2, the hot method Pvdf Microporous Hollow Fiber Membrane prepared of the inventive method, its external diameter is 1.2 ~ 1.6mm, and wall thickness is 290 ~ 380 μm.Its section is co-continuous network, asymmetric pore structure, and hole height is through, be evenly distributed, and outer surface aperture is in 20 ~ 50 nanometers.Be 25 DEG C in temperature, under 0.1MPa pressure, pure water flux is 400 ~ 850L/m
2h, tensile strength of fiber 5.0 ~ 8.5MPa, elongation at break 89 ~ 110%.The Structure and Properties of film shows after tested, and hot method Pvdf Microporous Hollow Fiber Membrane of the present invention is adapted at applying in municipal drinking water process.Film retain height, to produce water water quality good, not fracture of wire in using, stable performance.
3, the hot method Pvdf Microporous Hollow Fiber Membrane prepared of the inventive method, film good hydrophilic property, has excellent antifouling property.Use in Practical Project and prove, film not easily pollutes, and the regular maintenance cleaning frequency is 2 ~ 3 times of other similar film product, and maintenance operation expense is low.
Accompanying drawing explanation
Fig. 1 is the outer surface electromicroscopic photograph of hot method Pvdf Microporous Hollow Fiber Membrane prepared by the inventive method.
Fig. 2 is the section electromicroscopic photograph of hot method Pvdf Microporous Hollow Fiber Membrane prepared by the inventive method.
Detailed description of the invention
The preparation method of the hot method Pvdf Microporous Hollow Fiber Membrane for drinking water treatment that the present invention proposes, comprises the following steps:
(1) Kynoar and polyether sulfone are carried out drying respectively in dryer, the temperature of oven dry 80 ~ 90 DEG C, drying time is 24 ~ 36 hours;
(2) for the preparation of the blended polymer solution of masking:
In blended polymer solution, the mass percent of each component is:
After Kynoar, polyether sulfone, PEG400, triethyl phosphate and calcium chloride are weighed according to the above ratio, be placed in stirred tank, carry out stirring, dissolving at the temperature of 140 ~ 155 DEG C, mixing time is 14 ~ 16 hours, speed of agitator 90 ~ 110 revs/min, makes uniform blended polymer solution;
(3) the extruding and be shaped of hollow-fibre membrane, detailed process is as follows:
(3-1) blended polymer solution in step (2) is sent in double screw extruder by spinning pump, the charging rate of raw material is 15 ~ 20Kg/ hour, the temperature of extruder 6 sections all sets unanimously, it is 140 ~ 155 DEG C, extrusion temperature scope is 140 ~ 155 DEG C, and screw speed is 90 ~ 120 revs/min;
(3-2) blended polymer solution is after double screw extruder is extruded, successively through filter and spinning pump, extrude from the annular die of spinning-drawing machine, form the as-spun fibre of hollow, the external diameter of described annular die is 5 millimeters, internal diameter is 4.2 millimeters, and annular die center passes into nitrogen, and the pressure of nitrogen is 30 ~ 60 millimeter of water (mmH
2o);
(3-3) above-mentioned hollow as-spun fibre is lower the temperature in the air of 10 ~ 20 DEG C in temperature, the distance that sky is walked is 10 ~ 30 centimetres, then enter in cold extraction liquid bath through cold extraction liquid cooling curing, through winder rolling, make hollow-fibre membrane intermediate, the rolling speed of winder 15 ~ 20 ms/min, described cold extraction liquid is the mixed liquor of water and glycerine, in mixed liquor, the mass percent concentration of water is 0 ~ 50wt%, the mass percent concentration of glycerine is 50 ~ 100wt%, and the temperature of mixed liquor is 30 ~ 40 DEG C;
(4) hollow-fibre membrane intermediate step (3) obtained immerses in ultra-pure water, and remove the diluent mixture in film, the water temperature of ultra-pure water is 30 ~ 45 DEG C, and ultrapure electrical conductivity of water is 10 μ S/cm, and leaching time is 10 ~ 12 hours;
(5) the hollow-fibre membrane intermediate removing diluent of step (4) is at room temperature dried, obtain Pvdf Microporous Hollow Fiber Membrane.
In above-mentioned preparation method, in described blended polymer solution, the mass ratio of each component is:
Polyether sulfone/Kynoar=0.2 ~ 0.27,
PEG400/triethyl phosphate=0.22 ~ 0.62,
(Kynoar+polyether sulfone)/(Kynoar+polyether sulfone+PEG400+triethyl phosphate+calcium chloride)=0.25 ~ 0.38,
Calcium chloride/(Kynoar+polyether sulfone)=0.011 ~ 0.0263.
In above-mentioned preparation method, the weight average molecular weight of described Kynoar is 370000, and the weight average molecular weight of polyether sulfone is 50000.
In the preparation method of hot method Pvdf Microporous Hollow Fiber Membrane of the present invention, each raw material is by percentage to the quality:
Meanwhile, wherein the mass ratio of each composition is:
P
2/P
1=0.2～0.27，D
1/D
2=0.22～0.62，（P
1+P
2）/（P
1+P
2+D
1+D
2+A）=（25～38）wt%，A/（P
1+P
2）=0.011～0.0263
The present invention adopt Kynoar (PVDF) good toughness, have good chemical stability, the characteristics such as solvent resistant, acid and alkali-resistance, resistance to oxidation are the preferred material of municipal drinking water treatment process.
The tensile break strength of PVDF material is low, for strengthening the tensile strength of pvdf membrane, adopts polyether sulfone (PES) as the material preparing alloy film in the present invention.Polyether sulfone (PES) is the engineering material that a kind of temperature tolerance is good.Intensity is high, and the pH value scope of application is wide, and can apply in the system of PH=1 ~ 13, resistance to oxidation, chemically-resistant is cleaned, and chlorine resistance is good, acid-alkali-corrosive-resisting.Adopt that PVDF and PES is blended prepares alloy film, be convenient to the advantage that performance is respective, obtain the hollow fiber ultrafiltration membrane of function admirable.
The present invention is blended by PVDF and PES, by the ratio of telomerized polymer, prepares the high strength of the different pore size of three-dimensional interpenetrating polymer network structure, anti-pollution, corrosion resistant hot method Pvdf Microporous Hollow Fiber Membrane.Blending ratio is determined, at PES/PVDF blending ratio P by the compatibility studying alloy system
2/ P
1be experimental study display under 10/90,20/80,30/70,40/60,50/50,60/40,70/30 condition, this co-mixing system is partially compatible system, works as P
2/ P
1during >0.27, Miscibility is deteriorated, film forming difficulty, therefore P in the present invention
2/ P
1≤ 0.27.
The present invention adopts CaCl
2as masking additive, be to utilize CaCl
2perforating action, improve the permeability of film.
In preparation method of the present invention, the Kynoar used, polyether sulfone, PEG400, triethyl phosphate and calcium chloride are all commercial goods, wherein the manufacturer of Kynoar, polyether sulfone is U.S. SOLVAY(Su Wei) company, the purchase shop of other raw material is traditional Chinese medicines group chemical reagent Beijing Co., Ltd.
Below introduce embodiments of the invention:
Embodiment 1:
(1) pretreatment of polymeric material:
By Kynoar PVDF(molecular weight 370000), polyether sulfone (molecular weight 50000) carries out drying, the temperature of oven dry 85 DEG C respectively in dryer.
(2) preparation of blended polymer solution:
By the Kynoar P of having dried
1, polyether sulfone P
2, PEG400 D1, triethyl phosphate D
2and addition of C aCl
2after weighing by mass percentage, be placed in batching kettle, its mass percent (wt%) is respectively P
1: P
2: D
1: D
2: A=25:5:19.5:50:0.5, at the temperature of 150 DEG C, carry out stirring and dissolving, mixing time 15 hours, speed of agitator is 100 revs/min, is dissolved into uniform blended polymer solution;
(3) the extruding of hollow-fibre membrane, be shaped:
(3-1) the blended polymer solution in step (2) is sent in double screw extruder by spinning pump, the charging rate of raw material is 15 kgs/hour, and the temperature of extruder 6 sections all sets unanimously, and extrusion temperature is 150 DEG C, screw speed is 100 revs/min, and die temperature is 150 DEG C;
(3-2) blended polymer solution is after double screw extruder is extruded, and successively through filter, spinning pump, extrude from annular die, forms the as-spun fibre of hollow.The external diameter 5 millimeters (mm) of described annular die, internal diameter is 4.2 millimeters (mm).The pressure that annular die center passes into nitrogen is 50 millimeter of water (mmH
2o);
(3-3) above-mentioned hollow as-spun fibre is lower the temperature in the air of 15 DEG C in temperature, and the distance that sky is walked is 30 centimetres (cm), to enter in cold extraction liquid bath through cold extraction liquid cooling curing, through winder rolling, makes hollow-fibre membrane intermediate.Rolling speed 15 ms/min; The mixed liquor that described cold extraction liquid is both water and glycerine, the temperature of cold extraction mixed liquor is 40 DEG C, and in cold extraction mixed liquor, the mass percent concentration of water is 20wt%, and the mass percent concentration of glycerine is 80wt%;
(4) leaching of diluent: immersed in ultra-pure water by the hollow-fibre membrane intermediate in (3), remove the diluent mixture in film, water temperature is 45 DEG C, and leaching time is 10 hours;
(5) dry: at room temperature drying removing the doughnut after diluent in (4), obtaining Pvdf Microporous Hollow Fiber Membrane goods.
The film outer surface average pore size of these goods is 30nm, and fiber outer diameter is 1.6mm, and wall thickness is 370 μm.Through scanning electronic microscope observation, film section be three-dimensional interpenetrating polymer network, asymmetric pore structure as shown in Figure 1, as can be seen from Figure 2, the section structure of Pvdf Microporous Hollow Fiber Membrane is continuous, even aperture distribution, hole height is through, film outward flange aperture is less than film section hole, and bore diameter gradient distributes, outer little, greatly interior, effectively can remove the colloid in water, microorganism, macromolecular substances.Illustrate, the contamination resistance of film strengthens, and is convenient to cleaning.Temperature be 25 DEG C, under 0.1MPa pressure, pure water flux is 650L/m
2h, tensile strength of fiber is 6.9MPa, elongation at break 101%.
Main preparation process condition and the film properties of embodiment of the present invention 2-6 is provided below in conjunction with table 1, but the content of each composition of the present invention is not limited to listed numerical value in this table, and it should be noted that, although listed file names with some other parameter in table 1, these Parameter Conditions have been described as necessary condition.For the present invention, the content of core is to improve film formula of liquid, and therefore, other parameters listed file names with in table 1 are just in order to provide about technical information of the present invention in more detail, be all preferred condition, described as necessary condition of the present invention.
The formulation ratio of table 1: embodiment 2-6, main preparation process condition and film properties
Claims (3)
1., for a preparation method for the hot method Pvdf Microporous Hollow Fiber Membrane of drinking water treatment, it is characterized in that the method comprises the following steps:
(1) Kynoar and polyether sulfone are carried out drying respectively in dryer, the temperature of oven dry 80 ~ 90 DEG C, drying time is 24 ~ 36 hours;
(2) for the preparation of the blended polymer solution of masking:
In blended polymer solution, the mass percent of each component is:
After Kynoar, polyether sulfone, PEG400, triethyl phosphate and calcium chloride are weighed according to the above ratio, be placed in stirred tank, carry out stirring, dissolving at the temperature of 140 ~ 155 DEG C, mixing time is 14 ~ 16 hours, speed of agitator 90 ~ 110 revs/min, makes uniform blended polymer solution;
(3) the extruding and be shaped of hollow-fibre membrane, detailed process is as follows:
(3-1) blended polymer solution in step (2) is sent in double screw extruder by spinning pump, the charging rate of raw material is 15 ~ 20Kg/ hour, the temperature of extruder 6 sections all sets unanimously, it is 140 ~ 155 DEG C, extrusion temperature scope is 140 ~ 155 DEG C, and screw speed is 90 ~ 120 revs/min;
(3-2) blended polymer solution is after double screw extruder is extruded, successively through filter and spinning pump, extrude from the annular die of spinning-drawing machine, form the as-spun fibre of hollow, the external diameter of described annular die is 5 millimeters, internal diameter is 4.2 millimeters, and annular die center passes into nitrogen, and the pressure of nitrogen is 30 ~ 60 millimeters of water;
(3-3) above-mentioned hollow as-spun fibre is lower the temperature in the air of 10 ~ 20 DEG C in temperature, the distance that sky is walked is 10 ~ 30 centimetres, then enter in cold extraction liquid bath through cold extraction liquid cooling curing, through winder rolling, make hollow-fibre membrane intermediate, the rolling speed of winder 15 ~ 20 ms/min, described cold extraction liquid is the mixed liquor of water and glycerine, in mixed liquor, the mass percent concentration of water is 0 ~ 50wt%, the mass percent concentration of glycerine is 50 ~ 100wt%, and the temperature of mixed liquor is 30 ~ 40 DEG C;
(4) hollow-fibre membrane intermediate step (3) obtained immerses in ultra-pure water, and remove the diluent mixture in film, the water temperature of ultra-pure water is 30 ~ 45 DEG C, and ultrapure electrical conductivity of water is 10 μ S/cm, and leaching time is 10 ~ 12 hours;
(5) the hollow-fibre membrane intermediate removing diluent of step (4) is at room temperature dried, obtain Pvdf Microporous Hollow Fiber Membrane.
2. the preparation method of Pvdf Microporous Hollow Fiber Membrane as claimed in claim 1, is characterized in that the mass ratio of each component in wherein said blended polymer solution is:
Polyether sulfone/Kynoar=0.2 ~ 0.27,
PEG400/triethyl phosphate=0.22 ~ 0.62,
(Kynoar+polyether sulfone)/(Kynoar+polyether sulfone+PEG400+triethyl phosphate+calcium chloride)=0.25 ~ 0.38,
Calcium chloride/(Kynoar+polyether sulfone)=0.011 ~ 0.0263.
3. the preparation method of Pvdf Microporous Hollow Fiber Membrane as claimed in claim 1, it is characterized in that the weight average molecular weight of wherein said Kynoar is 370000, the weight average molecular weight of polyether sulfone is 50000.
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| CN102764595A (en) * | 2011-05-03 | 2012-11-07 | 吕晓龙 | Polyvinylidene fluoride separation membrane and its preparation method |
| CN102366714B (en) * | 2011-10-21 | 2013-08-21 | 湖州森蓝环境工程有限公司 | Preparation method for hollow fiber microporous membrane with small aperture and high flux and product thereof |
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| CN103638830A (en) | 2014-03-19 |
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